Functional Group Effects on the Electrochemical Properties of Carboranethiol Monolayers on Au(111) As Studied by Density Functional Theory: Implications for Organic Electronics

Yortanli, Merve
Danışman, Mehmet Fatih
Mete, Ersen
Positional isomers of dicarba-doso-dodecaboranethiols with various functional groups (-NO2, -CHO, -CONH2, -F, -Cl, and -OH) were considered on Au(111) forming (3 x 3) and (5 x 5) structures. Dispersion corrected density functional theory calculations reveal the influence of functional groups on the adsorption characteristics of these carboranethiols depending on the coverage. Functionalized molecules not only possess fascinating chemical and electronic properties but also show stronger chemisorption profiles on gold in relation to the pristine precursors. Molecular dipole moments which can be modified by functional groups were found to be effective in tunability of the work function of deposited surfaces. Results indicate that densely packed adsorption geometries in which functional groups lean toward back of adjacent molecules allowing H-bonding are energetically favorable and enhance stability and ordering of constituents in self-assembled monolayers. Carboranethiols with functional groups are promising to enrich the surface electrochemical properties of resulting surfaces.


Investigation of carboxyl-functionalized self-assembled monolayers on gold surfaces.
Görgülü, Salih; Danışman, Mehmet Fatih; Department of Chemistry (2020)
Thiolated derivatives of dicarba-closo-dodecaborane, HS-C 2 B 10 H 11 (carboranethiol, CT), with icosahedral molecular structure are one of the promising candidates for self-assembled monolayer (SAM) applications. CT SAMs possess various advantages relative to their organic counterparts, such as high stability towards chemical, oxidative and thermal degradations as well as having fewer defects. In this study unfunctionalized CT SAMs (M1, M9) and carboxylic group functionalized CT SAMs (M1C, M9C) as well as ...
Chemisorption of 3-aminopropyltrimethoxysilane on Si(001)-(2 x 2)
Demirel, G.; Cakmak, M.; Caykara, T.; Ellialtıoğlu, Süleyman Şinasi (2007-10-18)
The results of an ab initio calculation, based on pseudopotentials and the density functional theory, for the atomic and electronic structures of the chemisorption of 3-aminopropyltrimethoxysilane (APTS) on the Si(001)-(2 x 2) surface are presented. Two possible models for the chemisorption location of the APTS molecule are considered on the hydroxylated Si(001)-(2 x 2) surface: (i) an above-pedestal position (intra-row) between adjacent Si dimers and (ii) an above-hollow position. The first case is found t...
YILMAZ, H (1992-05-25)
The geometries of the low-lying isomers of phosphorus P2 to P10 were calculated using the semiempirical modified neglect of diatomic overlap method. It was found that, in those cases (P2 and P4) where spectroscopic data are available, the bond strengths are overestimated. The binding energies were found to be underestimated in those cases (P2, P3 and P4) where thermodynamically derived values for the gas phase are available. A roof-shaped tetramer is a prominent structural unit in low-lying states of P5, P6...
Free radical scavenging and antioxidative properties of 'silibin' complexes on microsomal lipid peroxidation
Basaga, H; Poli, G; Öztekin, Ceren; Aras, I (1997-03-01)
The antioxidant properties of silibin complexes, the water-soluble form silibin dihemisuccinate (SDH), and the lipid-soluble form, silibin phosphatidylcholine complex known as IdB 1016, were evaluated by studying their abilities to react with the superoxide radical anion (O-2(-)), and the hydroxyl radical (OH.). In addition, their effect on pulmonary and hepatic microsomal lipid peroxidation had been investigated. Superoxide radicals were generated by the PMS-NADH system and measured by their ability to red...
A van der Waals density functional investigation of carboranethiol self-assembled monolayers on Au(111)
Yılmaz, Ayşen; Danışman, Mehmet Fatih (2016-05-14)
Isolated and full monolayer adsorption of various carboranethiol (C2B10H12S) isomers on the gold(111) surface has been investigated using both the standard and van der Waals density functional theory calculations. The effect of different molecular dipole moment orientations on the low energy adlayer geometries, the binding characteristics and the electronic properties of the self-assembled monolayers of these isomers has been studied. Specifically, the binding energy and work function changes associated wit...
Citation Formats
M. Yortanli, M. F. Danışman, and E. Mete, “Functional Group Effects on the Electrochemical Properties of Carboranethiol Monolayers on Au(111) As Studied by Density Functional Theory: Implications for Organic Electronics,” ACS APPLIED NANO MATERIALS, vol. 5, no. 8, pp. 11185–11193, 2022, Accessed: 00, 2022. [Online]. Available: